EP1832609A2 - Procédé de préparation d'un copolymère à base d'une oléfine non-polaire et d'une oléfine polaire, et le copolymère ainsi obtenu - Google Patents

Procédé de préparation d'un copolymère à base d'une oléfine non-polaire et d'une oléfine polaire, et le copolymère ainsi obtenu Download PDF

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EP1832609A2
EP1832609A2 EP06021629A EP06021629A EP1832609A2 EP 1832609 A2 EP1832609 A2 EP 1832609A2 EP 06021629 A EP06021629 A EP 06021629A EP 06021629 A EP06021629 A EP 06021629A EP 1832609 A2 EP1832609 A2 EP 1832609A2
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group
compound
groups
formula
transition metal
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EP1832609A3 (fr
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Yoshihisa Inoue
Shigekazu Matsui
Yasuhiko Suzuki
Yasunori Yoshida
Yukihiro Takagi
Terunori Fujita
Tomoaki Matsugi
Takashi Nakano
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond

Definitions

  • the present invention relates to a process for producing a polar olefin copolymer and a polar olefin copolymer obtained by the process. More particularly relates to a process for producing a polar olefin copolymer comprising copolymerizing a non-polar olefin and a polar olefin in the presence of a specific catalyst and a polar olefin copolymer obtained by the process.
  • the olefin polymer is generally excellent in mechanical properties, and hence has widely been employed in varied fields such as ones of molded products of all sorts. However, since the demands for physical properties of olefin polymers have been diversified recently, olefin polymers with various properties have increasingly been desired.
  • a polar olefin copolymer obtained by copolymerizing a non-polar olefin and a polar olefin to provide properties which cannot be expected in a polymer consisting of non-polar olefins only.
  • Radical polymerization method is well known as a conventional process for producing a polar olefin copolymer by copolymerizing a non-polar olefin and a polar olefin, and for example, ethylene-vinyl acetate copolymers and ethylene-acrylic ester copolymers have been produced by this method.
  • An object of the present invention is to provide a process for producing a polar olefin copolymer capable of obtaining a polar olefin copolymer with excellent properties under mild polymerization conditions, and also to provide a polar olefin copolymer obtained by the process.
  • the process for preparing a polar olefin copolymer of the present invention comprises:
  • the transition metal compound of the formula (1) is preferably a compound of a transition metal selected from Groups 4, 5, 6 and 11 of the periodic table.
  • the other embodiment of the process for producing a polar olefin copolymer of the invention comprises:
  • the other embodiment of the process for producing a polar olefin copolymer of the invention comprises:
  • R 21 to R 28 may be the same or different, they are each a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a heterocyclic compound residual group, a silicon-containing group, a germanium-containing group or a tin-containing group, two or more of them may be bonded to each other to form a ring.
  • the transition metal compound of the formula (c') is preferably a compound of a transition metal selected from Groups 4, 5, 6 and 11 of the periodic table.
  • the other embodiment of the process for producing a polar olefin copolymer of the invention comprises:
  • the other embodiment of the process for producing a polar olefin copolymer of the invention comprises:
  • the other embodiment of the process for producing a polar olefin copolymer of the invention comprises:
  • the transition metal compound of the formula (VI) is preferably a compound of a transition metal selected from Groups 4, 5, 6 and 11 of the periodic table.
  • the polar olefin copolymer of the present invention is obtained by any of the above processes.
  • a compound which reacts with a reaction product (A1) to form an ion pair a compound which reacts with a reaction product (A2) to form an ion pair, a compound which reacts with a reaction product (A3) to form an ion pair, a compound which reacts with a transition metal compound (A4) to form an ion pair, a compound which reacts with a transition metal compound (A5) to form an ion pair and a compound which reacts with a transition metal compound (A6) to form an ion pair are referred to as "ionizing ionic compound".
  • the process for preparing a polar olefin copolymer according to the invention comprises:
  • the transition metal compound (A0) is represented by the following formula (1) L m MX n (1)
  • M is a transition metal atom selected from Groups 3 to 11, preferably Groups 4, 5, 6 and 11, of the periodic table.
  • transition metal atoms include scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper and silver.
  • transition metal atoms selected from Groups 4, 5, 6 and 11 of the periodic table, such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper and silver, and more preferable are titanium, vanadium and chromium.
  • m is an integer of 1 to 6, preferably an integer of 1 to 4.
  • n is a number satisfying a valence of M, specifically an integer of 0 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • M is the same transition metal atom selected from Groups 3 to 11 of the periodic table as M in the formula (1).
  • This ligand L may take any coordination form to the metal so long as the coordination energy difference ⁇ E is not more than 50 kJ/mol.
  • the coordination forms include covalent bond, coordinate bond, ionic bond and hydrogen bond.
  • the ligand L may be a monodentate ligand or a polydentate ligand such as a bidentate ligand coordinated to the transition metal atom M, and to the metal, any atom of the ligand L may be coordinated.
  • a is a number of the ligands L, and b is an electric charge of the compound in the brackets [ ]. b is 0 or +1. a is determined by the ligand L and a valence of the transition metal atom M, and is selected from integers of 1 to 3 so that the electric charge of the compound [L a -M-Me] can be 0 or +1.
  • Me is a methyl group.
  • the value obtained by subtracting the total sum of the whole energy, as determined by a density functional method, of the compounds on the left-hand member from the whole energy, as determined by a density functional method, of the compound on the right-hand member in the chemical formula (2) and the value obtained by the same subtraction in the chemical formula (3) are defined as coordination energy E 1 of ethylene and coordination energy E 2 of methyl acrylate, respectively.
  • the density functional method used herein means calculation using Program ADF2000.01 and using BLYP method.
  • the structure of each compound in the chemical formulas (2) and (3) is optimized, and the whole energy of each compound having the optimized structure is calculated. Then, the total sum of the whole energy of the compounds on the left-hand member in the chemical formula (2) is subtracted from the whole energy of the compound on the right-hand member in the chemical formula (2), and the value obtained is taken as coordination energy E 1 of ethylene. Likewise, the total sum of the whole energy of the compounds on the left-hand member in the chemical formula (3) is subtracted from the whole energy of the compound on the right-hand member in the chemical formula (3), and the value obtained is taken as coordination energy E 2 of methyl acrylate.
  • a triple zeta type function is used as a basis function, for atoms bonded to the metal atom among a methyl group coordinated to the central metal, all atoms in ethylene and methyl acrylate and atoms in the ligand L, double zeta type functions are used as basis functions; and for the other atoms, single zeta type functions are used as basis functions.
  • a structure in which oxygen of the carbonyl group is coordinated to the central metal M of the complex is shown as a coordination structure of methyl acrylate, and the coordination structure is determined by the result of the structure optimization calculation. As a result of the calculation, if the olefinic carbon of methyl acrylate and the central metal M have mutual interaction, the whole energy of the compound is calculated using the structure.
  • a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising a compound of a transition metal selected from Groups 3 to 11 of the periodic table, said compound containing each ligand L having a difference ⁇ E, between the coordination energy of ethylene and the coordination energy of methyl acrylate, of not more than 50 kJ/mol and being represented by the above formula (1).
  • Each of the coordination energy E 1 of ethylene and the coordination energy E 2 of methyl acrylate indicates a degree of stabilization due to coordination of each monomer to the transition metal, and the difference ⁇ E is a measure of difference between the degrees of stabilization.
  • the difference ⁇ E is not more than 50 kJ/mol, preferably not more than 30 kJ/mol, more preferably not more than 20 kJ/mol.
  • X denotes a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residual group, a silicon-containing group, a germanium-containing group or a tin-containing group.
  • M and X are bonded through a double bond.
  • halogen atoms examples include fluorine, chlorine, bromine and iodine.
  • hydrocarbon groups examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups of 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; and aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl and phenanthryl. These hydrocarbon groups may also include halogenated hydrocarbon groups, specifically those groups of 1 to 30 carbon atom
  • oxygen-containing groups examples include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; an acetoxy group; a carbonyl group; an acetylacetonato group (acac); and an oxo group.
  • sulfur-containing groups examples include sulfonato groups such as methylsulfonato, trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato, p-toluenesulfonato, trimethylbenzenesulfonato, triisobutylbenzenesulfonato, p-chlorobenzenesulfonato and pentafluorobenzenesulfonato; sulfinato groups such as methylsulfinato, phenylsulfinato, benzylsulfinato, p-toluenesulfinato, trimethylbenzenesulfinato and pentafluorobenzenesulfinato; an alkylthio group; an arylthio group; a sulfate group; a sulfide group;
  • nitrogen-containing groups include an amino group; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; arylamino or alkylarylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino; and alkyl or arylamine groups such as trimethyamine, triethylamine, triphenylamine, N,N,N',N'-tetramethylethylenediamine (tmeda) and N,N,N',N'-tetraphenylpropylenediamine (tppda).
  • alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino
  • boron-containing groups examples include BR 4 (R is hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom or the like).
  • Examples of the aluminum-containing groups include AlR 4 (R is hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom or the like).
  • Examples of the phosphorus-containing groups include trialkylphosphine groups such as trimethylphosphine, tributylphosphine and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tritolylphosphine; phosphite groups (phosphido groups) such as methylphosphite, ethylphosphite and phenylphosphite; a phosphonic acid group; and a phosphinic acid group.
  • trialkylphosphine groups such as trimethylphosphine, tributylphosphine and tricyclohexylphosphine
  • triarylphosphine groups such as triphenylphosphine and tritolylphosphine
  • phosphite groups phosphido groups
  • a phosphonic acid group such as methylphosphite, ethylphosphi
  • halogen-containing groups examples include fluorine-containing groups such as PF 6 and BF 4 ; chlorine-containing groups such as ClO 4 and SbCl 6 ; and iodine-containing groups such as IO 4 .
  • heterocyclic compound residual groups examples include residual groups of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran and sulfur-containing compounds such as thiophene; and these heterocyclic compound residual groups which are further substituted with substituents such as alkyl or alkoxy groups of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • silicon-containing groups examples include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.
  • silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritoly
  • germanium-containing groups examples include groups wherein silicon is replaced with germanium in the aforesaid silicon-containing groups.
  • tin-containing groups examples include groups wherein silicon is replaced with tin in the aforesaid silicon-containing groups.
  • plural atoms or groups indicated by X may be the same or different, and plural groups indicated by X may be bonded to each other to form a ring.
  • the bond form between X and the transition metal atom M is not specifically restricted, and examples of the bond forms between X and the transition metal atom M include covalent bond, coordinate bond, ionic bond and hydrogen bond.
  • the ligands L and the transition metal atoms M in the formula (1) is quite the same as those in the chemical formulas (2) and (3), including the valence of the metal, but the numbers a of the ligands and n in those formulas are not necessarily equal to each other.
  • the reaction product (A1) is a reaction product of a compound (C) of a transition metal selected from Groups 4, 5, 6 and 11 of the periodic table which is represented by the following formula (c), and a compound represented by the following formula (I).
  • M' is a transition metal atom selected from Groups 4, 5, 6 and 11 of the periodic table, and examples thereof include metal atoms of Group 4 such as titanium, zirconium and hafnium; metal atoms of Group 5 such as vanadium, niobium and tantalum; metal atoms of Group 6 such as chromium, molybdenum and tungsten; and metal atoms of Group 11 such as copper, silver and gold.
  • metal atoms of Group 4 such as titanium, zirconium and hafnium
  • metal atoms of Group 5 such as vanadium, niobium and tantalum
  • metal atoms of Group 6 such as chromium, molybdenum and tungsten
  • metal atoms of Group 11 such as copper, silver and gold.
  • titanium, vanadium and chromium are preferable.
  • X has the same meanings as that of X in the formula (1).
  • k is 2 or greater, plural groups indicated by X may be the same or different, and plural groups indicated by X may be bonded to each other to form a ring.
  • Bonding style between X and a transition metal atom M' has no specific restriction, and may be a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond or the like.
  • the k is a number satisfying a valence of M', and determined according to a valence of the transition metal M' and a valence of X so that these positive and negative valences are neutralized.
  • k is determined by dividing into two or more numbers in order that the positive and negative valences are neutralized.
  • a b 1 ⁇ k 1 + b 2 ⁇ k 2 .
  • the transition metal compound represented by the formula (c) becomes VOCl 3 or VO 2 Cl.
  • the transition metal compound represented by the formula (c) becomes [VO][SO 4 ].
  • transition metal compounds represented by the formula (c) include halides of transition metals such as TiCl 3 , TiCl 4 , TiBr 3 , TiBr 4 , ZrCl 4 , ZrBr 4 , HfBr 4 , HfCl 4 , VCl 4 , VCl 5 , VBr 4 , VBr 5 , NbCl 5 , NbBr 5 , TaCl 5 , TaBr 4 , CrCl 3 , CrCl 2 , MoCl 5 , MoCl 3 , WCl 6 , WCl 5 , CuCl 2 , CuBr 2 , AgCl 2 and AuCl 2 ; complex compounds of transition metal halides (e.g., TiCl 4 ⁇ 2(THF) and ZrCl 4 ⁇ 2(Et 2 O)) and electron donor compounds (e.g., tetrahydrofuran (THF), acetonitrile or die
  • M' is preferably titanium, vanadium, chromium or copper
  • X is preferably a halogen atom, an alkyl group, an oxygen-containing group or a nitrogen-containing group, more preferably a chlorine atom, a bromine atom or a methyl group.
  • the reaction product (A1) is a reaction product of the transition metal compound (C) represented by the formula (c) and the compound (A-i) represented by the following formula (I).
  • A is an oxygen atom (-O-), a sulfur atom (-S-), a selenium atom (-Se-) or a nitrogen atom having a substituent R 6 (-N(R 6 )-).
  • R 1 to R 6 may be the same or different, they are each a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a heterocyclic compound residual group, a silicon-containing group, a germanium-containing group or a tin-containing group.
  • the halogen atoms include fluorine, chlorine, bromine and iodine.
  • hydrocarbon groups examples include straight-chain or branched alkyl groups of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-pentyl and n-hexyl; straight-chain or branched alkenyl groups of 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl; straight-chain or branched alkynyl groups of 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl; cyclic saturated hydrocarbon groups of 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, such as
  • the hydrogen atom may be replaced with halogen, and examples of these halogenated hydrocarbon groups of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, include trifluoromethyl, pentafluorophenyl and chlorophenyl.
  • the hydrogen atom may also be replaced with another hydrocarbon group, and examples of these aryl-substituted alkyl groups include benzyl and cumyl.
  • hydrocarbon groups may have heterocyclic compound residual groups; oxygen-containing groups, such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonato group, a hydroxyl group, a peroxy group and a carboxylic anhydride group; nitrogen-containing groups, such as an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanato group, an amidino group, a diazo group and ammonium salts derived from an amino group; sulfur-containing groups, such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a
  • alkyl groups of 1 to 30 carbon atoms preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl and n-hexyl; aryl groups of 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenylyl; terphenylyl, phenanthryl and anthryl; and substituted aryl groups such as the above aryl groups which are substituted with 1 to 5 substituents such as halogen atoms, alkyl or alkoxy groups of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and aryl or aryloxy groups of 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.
  • the heterocyclic compound residual groups are cyclic groups containing 1 to 5 hetero atoms therein, and particular examples of the hetero atoms include O, N, S, P and B. Particular examples of the cyclic groups include monocyclic and polycyclic groups of 4 to 7 members, and preferable are monocyclic and polycyclic groups of 5 to 6 members.
  • residual groups of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine
  • residual groups of oxygen-containing compounds such as furan and pyran
  • residual groups of sulfur-containing compounds such as thiophen
  • substituents such as alkyl or alkoxy groups of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • the oxygen-containing groups are groups containing 1 to 5 oxygen atoms therein, but the above-mentioned heterocyclic residual groups are excluded. Similarly excluded from the oxygen-containing groups are groups containing a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom or a silicon atom, and having a direct bond of such an atom and an oxygen atom. Examples of the oxygen-containing groups include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxyl group, a peroxy group and a carboxylic anhydride group.
  • an alkoxy group, an aryloxy group, an acetoxy group, a carbonyl group and a hydroxyl group are preferable.
  • oxygen-containing groups contain carbon atoms, 1 to 30 carbon atoms are preferable, and 1 to 20 carbon atoms are more preferable.
  • the nitrogen-containing groups are groups containing 1 to 5 nitrogen atoms therein, but the above-mentioned heterocyclic residual groups are excluded.
  • the nitrogen-containing groups include an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanato group, an amidino group, a diazo group and ammonium salts derived from an amino group.
  • an amino group, an imino group, an amido group, an imido group, a nitro group and a cyano group are preferable.
  • these nitrogen-containing groups contain carbon atoms, 1 to 30 carbon atoms are preferable, and 1 to 20 carbon atoms are more preferable.
  • the sulfur-containing groups are groups containing 1 to 5 sulfur atoms therein, but the above-mentioned heterocyclic residual groups are excluded.
  • the sulfur-containing groups include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanato group, an isothiocyanato group, a sulfonato group, a sulfonamido group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group and a sulfenyl group, a sulfonate group and a sulfinate group.
  • a sulfonate group, a sulfinate group, an alkylthio group and an arylthio group are preferable.
  • these sulfur-containing groups contain carbon atoms, 1 to 30 carbon atoms are preferable, and 1 to 20 carbon atoms are more preferable.
  • the silicon-containing groups are groups containing 1 to 5 silicon atoms therein, and examples thereof include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group and a hydrocarbon-substituted siloxy group.
  • Particular examples of the hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl(pentafluorophenyl)silyl.
  • Particular examples of the hydrocarbon-substituted siloxy groups include trimethylsiloxy. When these silicon-containing groups contain carbon atoms, 1 to 30 carbon atoms are preferable, and 1 to 20 carbon atoms are more preferable.
  • the phosphorus-containing groups are groups containing 1 to 5 phosphorus atoms therein, but the above-mentioned heterocyclic residual groups are excluded.
  • Examples of the phosphorus-containing groups include a phosphino group, a phosphoryl group, a phosphothioyl group and a phosphono group.
  • the boron-containing groups are groups containing 1 to 5 boron atoms therein, but the above-mentioned heterocyclic residual groups are excluded.
  • Examples of the boron-containing groups include a boron substituted with an alkyl group, a boron substituted with an aryl group, a boron halide and a boron halide substituted with an alkyl group.
  • borons substituted with alkyl groups include (Et) 2 B-, (iPr) 2 B-, (iBu) 2 B-, (nC 5 H 11 ) 2 B-, C 8 H 14 B-(9-borabicyclononyl group); particular examples of the borons substituted with aryl groups include (C 6 H 5 ) 2 B-; particular examples of the boron halides include BCl 2 -; particular examples of the boron halides substituted with alkyl groups include (Et)BCl- and (iBu)BCl-. In these, Et denotes an ethyl group, iPr denotes an isopropyl group, and iBu denotes an isobutyl group.
  • Examples of the aluminum-containing groups include AlR 4 (R is hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom or the like).
  • germanium-containing groups or the tin-containing groups include groups wherein silicon is replaced with germanium or tin in the above-mentioned silicon-containing groups.
  • the heterocyclic compound residual group, the oxygen-containing group, the nitrogen-containing group, the sulfur-containing group, the boron-containing group, the germanium-containing group, the tin-containing group, the silicon-containing group and the phosphorus-containing group are each preferably the group wherein the characteristic atom group thereof is directly bonded to N, C or a carbon atom in A in the formula (I).
  • alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy;
  • preferred examples of the aryloxy groups include phenoxy, 2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy;
  • preferred examples of the acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl and p-methoxybenzoyl; and preferred examples of the ester groups include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.
  • amido groups include acetamido, N-methylacetamido and N-methylbenzamido
  • amino groups include alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino, and arylamino groups or alkylaryl groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino
  • preferred examples of the imido groups include acetimido and benzimido
  • preferred examples of the imino groups include methylimino, ethylimino, propylimino, butylimino and phenylimino.
  • alkylthio groups include methylthio and ethylthio; preferred examples of the arylthio groups include phenylthio, methylphenylthio and naphthylthio; preferred examples of the thioester groups include acetylthio, benzoylthio, methylthiocarbonyl and phenylthiocarbonyl; preferred examples of sulfonato ester groups include methylsulfonato, ethylsulfonato and phenylsulfonato; and preferred examples of the sulfonamido groups include phenylsulfonamido, N-methylsulfonamido and N-methyl-p-toluenesulfonamido.
  • sulfonate groups include methylsulfonato, trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato, p-toluenesulfonato, trimethylbenzenesulfonato, triisobutylbenzenesulfonato, p-chlorobenzenesulfonato and pentafluorobenzenesulfonato;
  • examples of the sulfinato groups include methylsulfinato, phenylsulfinato, benzylsulfinato, p-toluenesulfinato, trimethylbenzenesulfinato and pentafluorobenzenesulfinato.
  • examples of the phosphino groups include dimethylphosphino and diphenylphosphino; examples of the phosphoryl groups include methylphosphoryl, isopropylphosphoryl and phenylphosphoryl; examples of the phosphothioyl groups include methylphosphothioyl, isopropylphosphothioyl and phenylphosphothioyl; and examples of the phosphono groups include phosphate groups such as dimethylphosphate, diisopropylphosphate and diphenylphosphate, and a phosphoric acid group.
  • Two or more groups of R 1 to R 6 may be bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., a nitrogen atom), which rings may have a substituent respectively.
  • the compounds represented by the formula (I) in which R 3 and R 4 are bonded to form an aromatic ring are represented by the following forumula (I-a): wherein A, R 1 , R 2 and R 5 to R 10 have the same meanings respectively as those of A and R 1 to R 6 in the aforesaid formula (I).
  • R 1 , R 2 and R 5 to R 10 may be the same or different, and two or more of them may be bonded to each other to form a ring.
  • R 1 , R 2 , R 6 , R 11 to R 15 have the same meanings as those of R 1 to R 6 in the above formula (I), R 1 , R 2 , R 6 , R 11 to R 15 may be the same or different and two or more of them may be bonded to each other to form a ring.
  • reaction between the transition metal compound (C) and the compound represented by the formula (I) is carried out, for example, as follows.
  • transition metal compound (C) and the compound (I) are mixed at a low temperature in the presence of a solvent, and then stirred at a temperature of -78 °C to room temperature, or under reflux, for 1 to 48 hours.
  • any solvent generally used for such reaction is employable.
  • a polar solvent such as ether or tetrahydrofuran (THF)
  • a hydrocarbon solvent such as toluene
  • the reaction with the transition metal compound (C) may be conducted after the compound (I) has been contacted with a base to prepare a salt, or after the compound (I) has been contacted with a silicon compound to produce a silicon compound.
  • a base there may be enumerated basic alkali metal compounds such as n-butyllithium and sodium hydroxide; basic alkali earth metal compounds such as ethylmagnesium bromide; and organic bases such as triethylamine and pyridine.
  • the silicon compound there may be enumerated alkylsilylchlorides such as trimethylsilylchloride and triethylsilylchloride.
  • the reaction between the transition metal compound (C) and the compound (I) at least a part of X in the formula (c) is substituted with a ligand derived from the compound (I).
  • the number of such ligands can be adjusted by altering the charge ratio between the transition metal compound (C) and the compound (I).
  • the compound (I) is in an amount of usually 1 to 6 mol, preferably 1 to 4 mol, based on 1 mol of the transition metal compound (C).
  • two or more kinds of compounds (I) may be used, and a different kind of compound (I) may be added successively during the reaction process.
  • the compound in which plural kinds of ligands are coordinated to the transition metal can be synthesized.
  • the proportion of ligands coordinated to the transition metal can be adjusted by altering the charge ratio between two or more kinds of compounds (I).
  • R 1 to R 4 and R 6 in the compound (I) is a hydrogen atom; a substituent other than a hydrogen atom may be introduced in any stage of the reaction.
  • composition and structure of the reaction product (A1) can be confirmed by analyzing through elemental analysis, X-ray crystal structure analysis, mass spectrum, NMR, IR or the like.
  • reaction product (A1) contains the after-mentioned transition metal compound (IV), and as the case may be, contains also the compound in which a part of X in the formula (c) is substituted with a ligand derived from the compound (I) (the compound (A1-a)), the unreacted transition metal compound (C), the compound (I) and others.
  • reaction product (A1) may be used in the form of mixture without purification, or with purification by distillation, recrystallization or the like.
  • the metal in the compound contained in the obtained reaction product (A1) may be replaced with another transition metal selected from Groups 4, 5, 6 and 11 of the periodic table by a conventional procedure.
  • the residual halogen group may be converted into a hydrocarbon group, and the amido group may be converted into a halogen group.
  • the catalyst component (A2) is a reaction product of the transition metal compound (C) represented by the formula (c) and a compound represented by the following formula (II).
  • D denotes a nitrogen atom or a phosphorus atom.
  • R 11 to R 16 may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I).
  • the heterocyclic compound residual group, the oxygen-containing group, the nitrogen-containing group, the sulfur-containing group, the boron-containing group, the germanium-containing group, the tin-containing group, the silicon-containing group and the phosphorus-containing group are each preferably the group wherein the characteristic atom group thereof is directly bonded to N, a carbon atom, a carbon atom in Q, S or T, or D in the formula (II).
  • Two or more groups of R 11 to R 16 may be bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., a nitrogen atom), which rings may have a substituent respectively.
  • a hetero atom e.g., a nitrogen atom
  • reaction between the transition metal compound (C) and the compound represented by the formula (II) is carried out, for example, as follows.
  • transition metal compound (C) and the compound (II) are mixed at a low temperature in the presence of a solvent, and then stirred at a temperature of -78 °C to room temperature, or under reflux, for 1 to 48 hours.
  • the same solvents as previously cited for the preparation of the reaction product (A1) are employable.
  • the reaction with the transition metal compound (C) may be conducted after the compound (II) has been contacted with a base to prepare a salt, or after the compound (II) has been contacted with a silicon compound to produce a silicon compound.
  • the base and the silicon compound used in this case the same ones as previously cited for the preparation of the reaction product (A1) may be enumerated.
  • the reaction between the transition metal compound (C) and the compound (II) at least a part of X in the formula (c) is substituted with a ligand derived from the compound (II).
  • the number of such ligands can be adjusted by altering the charge ratio between the transition metal compound (C) and the compound (II).
  • the compound (II) is in an amount of usually 1 to 6 mol, preferably 1 to 4 mol, based on 1 mol of the transition metal compound (C).
  • two or more kinds of compounds (II) may be used, and a different kind of compound (II) may be added successively during the reaction process.
  • the compounds in which plural kinds of ligands are coordinated to the transition metal can be synthesized.
  • the proportion of ligands coordinated to the transition metal can be adjusted by altering the charge ratio between two or more kinds of.compounds (II).
  • R 11 to R 15 in the compound (II) is a hydrogen atom
  • a substituent other than a hydrogen atom may be introduced in any stage of the reaction.
  • composition and structure of the reaction product (A2) can be confirmed by analyzing through elemental analysis, X-ray crystal structure analysis, mass spectrum, NMR, IR or the like.
  • reaction product (A2) contains the after-mentioned transition metal compound (V), and as the case may be, contains also the compound in which a part of X in the formula (c) is substituted with a ligand derived from the compound (II) (the compound (A2-a)), the unreacted transition compound (C), the compound (II) and others.
  • reaction product (A2) may be used in the form of mixture without purification, or with purification by distillation, recrystallization or the like.
  • the metal in the compound contained in the obtained reaction product (A2) may be replaced with another transition metal selected from Groups 4, 5, 6 and 11 of the periodic table by a conventional procedure.
  • the residual halogen group may be converted into a hydrocarbon group, and the amido group may be converted into a halogen group.
  • the catalyst component (A3) is a reaction product of the transition metal compound (C') represented by the formula (c') and a compound represented by the following formula (III).
  • M is a transition metal atom selected from Groups 3 to 11, preferably Groups 4, 5, 6 and 11, of the periodic table, and specific examples thereof include scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper and silver.
  • transition metal atoms selected from Groups 4, 5, 6 and 11 of the periodic table, such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper and silver, and more preferable are titanium, vanadium and chromium.
  • X and k have the same meanings as those of X and k in the above formula (c).
  • k is 2 or greater, plural groups indicated by X may be the same or different, and plural groups indicated by X may be bonded to each other to form a ring.
  • A denotes an oxygen atom (-O-), a sulfur atom (-S-) or a selenium atom (-Se-), or a nitrogen atom having a substitutent R 26 (-N(R 26 )-).
  • R 21 to R 28 may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I).
  • the hetero-containing compound residual group, the oxygen-containing group, the nitrogen-containing group, the sulfur-containing group, the boron-containing group, the germanium-containing group, the tin-containing group, the silicon-containing group and the phosphorus-containing group are each preferably the group wherein the characteristic atom group thereof is directly bonded to N, a carbon atom or A in the formula (III).
  • Two or more groups of R 21 to R 28 may be bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., a nitrogen atom), which rings may have a substituent respectively.
  • reaction between the transition metal compound (C') and the compound represented by the formula (III) is carried out, for example, as follows.
  • transition metal compound (C') and the compound (III) are mixed at a low temperature in the presence of a solvent, and then stirred at a temperature of -78 °C to room temperature, or under reflux, for 1 to 48 hours.
  • the same solvents as previously cited for the preparation of the reaction product (A1) are employable.
  • R 28 in the formula (III) is a hydrogen atom so that the compound (III) has an active hydrogen group
  • the reaction with the transition metal compound (C') may be conducted after the compound (III) has been contacted with a base to prepare a salt, or after the compound (III) has been contacted with a silicon compound to produce a silicon compound.
  • the base and the silicon compound used in this case the same ones as previously cited for the preparation of the reaction product (A1) may be enumerated.
  • the reaction between the transition metal compound (C') and the compound (III) at least a part of X in the formula (c') is substituted with a ligand derived from the compound (III).
  • the number of such ligands can be adjusted by altering the charge ratio between the transition metal compound (C') and the compound (III).
  • the compound (III) is in an amount of usually 1 to 6 mol, preferably 1 to 4 mol, based on 1 mol of the transition metal compound (C').
  • two or more kinds of compounds (III) may be used, and a different kind of compound (III) may be added successively during the reaction process.
  • the compounds in which plural kinds of ligands are coordinated to the transition metal can be synthesized.
  • the proportion of ligands coordinated to the transition metal can be adjusted by altering the charge ratio between two or more kinds of compounds (III).
  • R 21 to R 27 in the compound (III) is a hydrogen atom
  • a substituent other than a hydrogen atom may be introduced in any stage of the reaction.
  • composition and structure of the reaction product (A3) can be confirmed by analyzing through elemental analysis, X-ray crystal structure analysis, mass spectrum, NMR, IR or the like.
  • reaction product (A3) contains the after-mentioned transition metal compound (VI), and as the case may be, contains also the compound in which a part of X in the formula (c') is substituted with a ligand derived from the compound (III) (the compound (A3-a)), the unreacted transition compound (C'), the compound (III) and others.
  • reaction product (A3) may be used in the form of mixture without purification, or with purification by distillation, recrystallization or the like.
  • the metal in the compounds contained in the obtained reaction product (A3) may be replaced with another transition metal selected from Groups 4, 5, 6 and 11 of the periodic table by a conventional procedure.
  • the residual halogen group may be converted into a hydrocarbon group, and the amide group may be converted into a halogen group.
  • the transition metal compound (A4) is a compound of a transition metal selected from Groups 4, 5, 6 and 11 of the periodic table which is represented by the following formula (IV): (wherein the dotted line (----) of N----M' means that a coordinate bond is formed, but a compound having no coordinate bond is also included in the present invention.)
  • M' has the same meaning as that of M' in the formula (c), and particularly preferable is a titanium atom, a vanadium atom, a chromium atom or a copper atom.
  • the m is an integer of 1 to 6, preferably an integer of 1 to 4.
  • A has the same meaning as that of A in the formula (I) .
  • R 1 to R 4 and R 6 have the same meanings as those of R 1 to R 6 in the formula (I)'.
  • R 1 to R 4 and R 6 Two or more groups of R 1 to R 4 and R 6 , preferably the adjacent groups thereof, may be bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., a nitrogen atom), which rings may have a substituent respectively.
  • m is 2 or greater
  • one group of R 1 to R 4 and R 6 contained in one ligand may be bonded to one group of R 1 to R 4 and R 6 contained in another ligand, and R 1 s, R 2 s, R 3 s, R 4 s or R 6 s may be the same or different.
  • n is a number satisfying a valence of M', and concretely an integer of 0 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • X has the same meaning as that of X in the formula (c).
  • n is 2 or greater, the plural groups indicated by X may be the same or different, and the plural groups indicated by X may be bonded to each other to form a ring.
  • transition metal compound represented by the formula (IV) wherein R 3 and R 4 are bonded to each other to form an aromatic ring is represented by the following formula (IV-a).
  • A, M', X, m and n have the same meanings respectively as those of A, M', X, m and n in the formula (IV).
  • R 1 , R 2 and R 6 to R 10 may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I). Two or more of R 1 , R 2 and R 6 to R 10 may be bonded to each other to form a ring.
  • transition metal compounds represented by the formula (IV) the compounds wherein m is 2, and one group of R 1 to R 4 and R 6 contained in any one ligand is bonded to one group of R 1 to R 4 and R 6 contained in another ligand are represented, for example, by the following formula (IV-b).
  • A, M', X and n have the same meanings respectively as those of A, M', X and n in the aforesaid formula (IV).
  • R 1 to R 4 and R 6 may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I). Two or more of R 1 to R 4 and R 6 may be bonded to each other to form a ring.
  • A' may be the same as, or different from A, and denotes an oxygen atom (-O-), a sulfur atom (-S-) or a selenium atom (-Se-), or a nitrogen atom having a bonding group R 6' (-N(R 6' )-).
  • R 1' to R 4' and R 6' may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I). Two or more of R 1' to R 4' and R 6' may be bonded to each other to form a ring. Further, R 1 to R 4 and R 6 may be the same as, or different from R 1' to R 4' and R 6' respectively.
  • Y denotes a bonding group or a single bond, in which at least one group selected from R 1 to R 4 is bonded to at least one group selected from R 1' to R 4' .
  • the bonding group desirably has a structure wherein the main chain consists of 3 or more atoms, preferably 4 to 20 atoms, more preferably 4 to 10 atoms.
  • the bonding group may have a substituent.
  • bondsing group indicated by Y there may be enumerated groups containing at least one element selected from oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin, boron and so on.
  • groups include chalcogen atom-containing groups such as -O-, -Sand -Se-; nitrogen or phosphorus atom-containing groups such as -NH-, -N(CH 3 ) 2 -, -PH- and -P(CH 3 ) 2 -; hydrocarbon groups of 1 to 20 carbon atoms such as -CH 2 -, -CH 2 -CH 2 -and -C(CH 3 ) 2 -; residual groups of cyclic unsaturated hydrocarbons of 6 to 20 carbon atoms such as benzene, naphthalene and anthracene; residual groups of heterocyclic compounds having 3 to 20 carbon atoms and containing hetero atoms such as pyridine, quinoline, thiophene and fur
  • A, M', X and n have the same meanings respectively as those of A, M', X and n in the formula (IV).
  • B 1 , R 2 and R 6 to R 10 may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I). Two or more of R 1 , R 2 and R 6 to R 10 may be bonded to each other to form a ring.
  • A' may be the same as, or different from A, and denotes an oxygen atom (-O-), a sulfur atom (-S-) or a selenium atom (-Se-), or a nitrogen atom having a bonding group R 6 ' (-N (R 6' )-).
  • R 1' , R 2' and R 6' to R 10' may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I). Two or more of R 1' , R 2' and R 6' to R 10' may be bonded to each other to form a ring. Further, R 1 , R 2 and R 6 to R 10 may be the same as, or different from R 1' , R 2' and R 6' to R 10' respectively.
  • Y denotes a bonding group or a single bond, in which at least one group selected from R 1 , R 2 and R 6 to R 10 is bonded to at least one group selected from R 1' , R 2' and R 6' to R 10' .
  • the bonding group desirably has a structure wherein the main chain consists of 3 or more atoms, preferably 4 to 20 atoms, more preferably 4 to 10 atoms.
  • the bonding group may have a substituent.
  • the bonding group indicated by Y there may be enumerated the same groups as indicated by Y in the formula (IV-b).
  • transition metal compounds represented by the above formula (IV) compounds in which R 3 , R 4 and R 5 are bonded to form an aromatic ring are represented by the following formula (IV-d).
  • M', X, m and n have the same meanings respectively as those of M', X, m and n in the formula (IV).
  • R 1 , R 2 and R 11 to R 15 may be the same or different and have the same meanings as those of R 1 to R 6 in the formula (I). Further, two or more of these R 1 , R 2 and R 11 to R 15 may be bonded to each other to form a ring.
  • transition metal compounds represented by the formula (IV), (IV-a), (IV-b), (IV-c) and (IV-d) are given below.
  • the compound in which such a metal of Group 4 is replaced with another metal of Group 4 may be included in the above examples.
  • a specific example is a Ti compound
  • the compound wherein Ti is replaced with Zr or Hf can also be enumerated.
  • the compound in which such a metal of Group 5 is replaced with another metal of Group 5 may be included in the above examples.
  • the compound wherein V is replaced with Nb or Ta can also be enumerated.
  • the compound in which such a metal of Group 6 is replaced with another metal of Group 6 may be included in the above examples.
  • a specific example is a Cr compound
  • the compound wherein Cr is replaced with Mo or W can also be enumerated.
  • the compound in which such a metal of Group 11 is replaced with another metal of Group 11 may be included in the above examples.
  • a specific example is a Cu compound
  • the compound wherein Cu is replaced with Ag or Au can also be enumerated.
  • the transition metal compound (A5) is a compound of a transition metal selected from Groups 4, 5, 6 and 11 of the periodic table which is represented by the following formula (V): (wherein the dotted line (----) of N----M' means that a coordinate bond is formed, but a compound having no coordinate bond is also included in the present invention.)
  • M' has the same meaning as that of M' in the formula (c), and particularly preferable is a titanium atom, a vanadium atom, a chromium atom or a copper atom.
  • D, Q, S and T have the same meanings respectively as those of D, Q, S and T in the formula (II).
  • the m is an integer of 1 to 6, preferably an integer of 1 to 4.
  • R 11 to R 15 may be the same or different, and have the same meanings as those of R 11 to R 16 in the formula (II). Two or more groups of R 11 to R 15 , preferably the adjacent groups thereof, may be bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., a nitrogen atom), which rings may have a substituent respectively.
  • m is 2 or greater, one group of R 11 to R 15 contained in any one ligand may be bonded to one group of R 11 to R 15 contained in another ligand, and R 11 s, R 12 s, R 13 s, R 14 s or R 15 s may be the same or different.
  • n is a number satisfying a valence of M', and concretely an integer of 0 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • X has the same meaning as that of X in the formula (c).
  • n is 2 or greater, the plural groups indicated by X may be the same or different, and the plural groups indicated by X may be bonded to each other to form a ring.
  • the compounds in which m is 2, and one group of R 11 to R 15 contained in any one ligand is bonded one group of R 11 to R 15 contained in another ligand are represented, for example, by the following forumula (V-a).
  • M', X, n, D, Q, S and T have the same meanings respectively as those of M', X, n, D, Q, S and T in the formula (V).
  • R 11 to R 15 may be the same or different, and have the same meanings as those of R 11 to R 16 in the formula (II). Two or more of R 11 to R 15 may be bonded to each other to form a ring.
  • D' may be the same as, or different from D, and denotes a nitrogen atom or a phosphorus atom.
  • R 11' to R 15' may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I). Two or more of R 11' to R 15' may be bonded to each other to form a ring. Further, R 11 to R 15 may be the same as, or different from R 11' to R 15' respectively.
  • Y denotes a bonding group or a single bond, in which at least one group selected from R 11 to R 15 is bonded to at least one group selected from R 11' to R 15' .
  • the bonding group desirably has a structure wherein the main chain consists of 3 or more atoms, preferably 4 to 20 atoms, more preferably 4 to 10 atoms.
  • the bonding group may have a substituent.
  • As the bonding group indicated by Y there may be enumerated the same groups as indicated by Y in the formula (IV-b).
  • transition metal compounds represented by the formula (V) or (V-a) are given below.
  • the compound in which such a metal of Group 4 is replaced with another metal of Group 4 may be included in the above examples.
  • a specific example is a Ti compound
  • the compound wherein Ti is replaced with Zr or Hf can also be enumerated.
  • the compound in which such a metal of Group 5 is replaced with another metal of Group 5 may be included in the above examples.
  • the compound wherein V is replaced with Nb or Ta can also be enumerated.
  • the compound in which such a metal of Group 6 is replaced with another metal of Group 6 may be included in the above examples.
  • a specific example is a Cr compound
  • the compound wherein Cr is replaced with Mo or W can also be enumerated.
  • the compound in which such a metal of Group 11 is replaced with another metal of Group 11 may be included in the above examples.
  • a specific example is a Cu compound
  • the compound wherein Cu is replaced with Ag or Au can also be enumerated.
  • the transition metal compound (A6) is a compound of a transition metal selected from Groups 3 to 11 of the periodic table which is represented by the following formula (VI): (wherein the dotted line (----) of N----M means that a coordinate bond is formed, but a compound having no coordinate bond is also included in the present invention.)
  • M has the same meaning as that of M in the formula (c'), and preferred is a transition metal atom selected from Group 4, 5, 6 and 11 of the periodic table such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper and silver, and particularly preferred is titanium, vanadium or chromium.
  • a transition metal atom selected from Group 4, 5, 6 and 11 of the periodic table such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper and silver, and particularly preferred is titanium, vanadium or chromium.
  • the m is an integer of 1 to 6, preferably an integer of 1 to 4.
  • A has the same meaning as that of A in the formula (III) .
  • R 21 to R 27 may be the same or different, and have the same meanings as those of R 21 to R 28 in the formula (III). Two or more groups of R 21 to R 27 , preferably the adjacent groups thereof, may be bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., a nitrogen atom), which rings may have a substituent respectively.
  • Two or more groups of R 21 to R 27 preferably the adjacent groups thereof, may be bonded to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., a nitrogen atom), which rings may have a substituent respectively.
  • R 21 to R 27 contained in any one ligand may be bonded to one group of R 21 to R 27 contained in another ligand, and R 21 s, R 22 s, R 23 s, R 24 s, R 25 s, R 26 s or R 27 s may be the same or different.
  • n is a number satisfying a valence of M, and concretely an integer of 0 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3.
  • X has the same meaning as that of X in the formula (c)'.
  • n is 2 or greater, the plural groups indicated by X may be the same or different, and the plural groups indicated by X may be bonded to each other to form a ring.
  • the compounds in which m is 2, and one group of R 21 to R 27 contained in any one ligand is bonded one group of R 21 to R 27 contained in another ligand are represented, for example, by the following formula (VI-a).
  • A, M, X and n have the same meanings respectively as those A, M, X and n in the formula (VI).
  • R 21 to R 27 may be the same or different, and have the same meanings as those of R 21 to R 28 in the formula (III). Two or more of R 21 to R 27 may be bonded to each other to form a ring.
  • A' may be the same as, or different from A, and denotes an oxygen atom (-O-), a sulfur atom (-S-) or a selenium atom (-Se-), or a nitrogen atom having a bonding group R 26' (-N(R 26' )-).
  • R 21' to R 27' may be the same or different, and have the same meanings as those of R 1 to R 6 in the formula (I). Two or more of R 21' to R 27' may be bonded to each other to form a ring. Further, R 21 to R 27 may be the same as, or different from R 21' to R 27' respectively.
  • Y denotes a bonding group or a single bond, in which at least one group selected from R 21 to R 27 is bonded to at least one group selected from R 21' to R 27' .
  • the bonding group desirably has a structure wherein the main chain consists of 3 or more atoms, preferably 4 to 20 atoms, more preferably 4 to 10 atoms.
  • the bonding group may have a substituent.
  • As the bonding group indicated by Y there may be enumerated the same groups as indicated by Y in the formula (IV-b).
  • transition metal compounds represented by the formula (VI) or (VI-a) are given below.
  • compounds in which the transition metal is replaced with another transition metal of the same Group may be enumerated.
  • a specific example is a Ti compound
  • the compound wherein Ti is replaced with Zr or Hf can also be enumerated.
  • a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising these transition metal compounds and at least one compound (B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy-compound and (B-3) an ionizing ionic compound.
  • transition metal compound (A0), (A3) or (A6) it is one of the preferred embodiments that a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising these transitin metal compounds and the component (B).
  • organometallic compound (B-1) examples include organometallic compounds containing metals of Group 1, Group 2, Group 12 and Group 13 of the periodic table, such as those described below.
  • organoaluminum compounds (B-1a) examples include:
  • organoaluminum compounds (B-1a) include:
  • organoaluminum compound (B-1a) is also employable.
  • organoaluminum compounds wherein two or more aluminum compounds are combined through a nitrogen atom, such as (C 2 H 5 ) 2 AlN(C 2 H 5 )Al(C 2 H 5 ) 2 .
  • Examples of the compounds (B-1b) include LiAl(C 2 H 5 ) 4 and LiAl (C 7 H 15 ) 4 .
  • organometallic compounds (B-1) include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium and butylethylmagnesium.
  • Combinations of compounds capable of producing the above-mentioned organoaluminum compounds in the polymerization system e.g., a combination of halogenated aluminum and alkyllithium and a combination of halogenated aluminum and alkylmagnesium, are also employable.
  • organometallic compounds (B-1) the organoaluminum compounds are preferable.
  • organometallic compounds (B-1) mentioned above are used singly or in combination of two or more kinds.
  • the organoaluminum oxy-compound (B-2) may be conventional aluminoxane or a benzene-insoluble organoaluminum oxy-compound such as exemplified in Japanese Patent Laid-Open Publication No. 78687/1990 .
  • the conventional aluminoxane can be prepared by, for example, the following processes, and is generally obtained as a hydrocarbon solvent solution.
  • the aluminoxane may contain a small amount of an organometallic component. Further, it is possible that the solvent or the unreacted organoaluminum compound is distilled off from the recovered solution of aluminoxane and the remainder is redissolved in a solvent or suspended in a poor solvent for aluminoxane.
  • organoaluminum compounds used for preparing the aluminoxane include the same organoaluminum compounds as previously described with respect to the organoaluminum compound (B-1a). Of these, preferable are trialkylaluminums and tricycloalkylaluminums. Particularly preferable is trimethylaluminum.
  • the organoaluminum compounds are used singly or in combination of two or more kinds.
  • solvents used for preparing the aluminoxane include aromatic hydrocarbons, such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions, such as gasoline, kerosine and gas oil; and halogenated products of these aromatic, aliphatic and alicyclic hydrocarbons (e.g., chlorinated or brominated products thereof). Also employable are ethers such as ethyl ether and tetrahydrofuran. Of the solvents, particularly preferable are aromatic hydrocarbons and aliphatic hydrocarbons.
  • the benzene-insoluble organoaluminum oxy-compound for use in the invention is preferably an organoaluminum oxy-compound containing an Al component which is soluble in benzene at 60 °C, in an amount of usually not more than 10 %, preferably not more than 5 %, particularly preferably not more than 2 %, in terms of Al atom. That is, the benzene-insoluble organoaluminum oxy-compound is preferably insoluble or sparingly soluble in benzene.
  • the organoaluminum oxy-compound is, for example, an organoaluminum oxy-compound containing boron and represented by the following formula (i): wherein R 20 is a hydrocarbon group of 1 to 10 carbon atoms; and each R 21 may be the same or different and is a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 10 carbon atoms.
  • the organoaluminum compound containing boron and represented by the formula (i) can be prepared by allowing an alkylboronic acid represented by the following formula (ii): R 20 -B-(OH) 2 (ii) wherein R 20 is the same group as described above, to react with an organoaluminum compound in an inert solvent at a temperature of -80 °C to room temperature for 1 minute to 24 hours under an inert gas atmosphere.
  • alkylboronic acids represented by the formula (ii) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and 3,5-bis(trifluoromethyl)phenylboronic acid.
  • alkylboronic acids are used singly or in combination of two or more kinds.
  • organoaluminum compounds to be reacted with the alkylboronic acid include the same organoaluminum compounds as previously described with respect to the organoaluminum compound (B-1a). Of these, preferable are trialkylaluminums and tricycloalkylaluminums. Particularly preferable are trimethylaluminum, triethylaluminum and triisobutylaluminum. These organoaluminum compounds are used singly or in combination of two or more kinds.
  • organoaluminum oxy-compounds (B-2) mentioned above are used singly or in combination of two or more kinds.
  • the ionizing ionic compound (B-3) includes a compound which reacts with the reaction product (A1) to form an ion pair, a compound which reacts with the reaction product (A2) to form an ion pair, a compound which reacts with the reaction product (A3) to form an ion pair, a compound which reacts with transition metal compound (A4) to form an ion pair, a compound which reacts with transition metal compound (A5) to form an ion pair, and a compound which reacts with transition metal compound (A6) to form an ion pair.
  • Any compound which forms an ion pair by the contact with at least the reaction products and the transition metal compounds is employable as the compound (B-3).
  • Examples of such compounds includes Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Patent Laid-Open Publications No. 501950/1989 , No. 502036/1989 , No. 179005/1991 , No. 179006/1991 , No. 207703/1991 and No. 207704/1991 , and U.S. Patent No. 5,321,106 .
  • a heteropoly compound and an isopoly compound may also be employed.
  • the Lewis acids are, for example, compounds represented by BR 3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, methyl or trifluoromethyl).
  • examples of such compounds include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron and tris(3,5-dimethylphenyl)boron.
  • the ionic compounds are, for example, compounds represented by the following formula (iii):
  • R 22 is H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, or the like.
  • R 23 to R 26 may be the same or different and are each an organic group, preferably an aryl group or a substituted aryl group.
  • Examples of the carbonium cations include trisubstituted carbonium cations, such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation and tri(dimethylphenyl)carbonium cation.
  • ammonium cations examples include trialkylammonium cations, such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations, such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations, such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.
  • trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri(n-butyl)ammonium
  • Examples of the phosphonium cations include triarylphosphonium cations, such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation and tri(dimethylphenyl)phosphonium cation.
  • R 22 is preferably carbonium cation or ammonium cation, particularly preferably triphenylcarbonium cation, N,N-dimethylanilinium cation or N,N-diethylanilinium cation.
  • ionic compound is a trialkyl-substituted ammonium salt, a N,N-dialkylanilinium salt, a dialkylammonium salt or a triarylphosphonium salt.
  • trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron
  • N,N-dialkylanilinium salts examples include N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron and N,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron.
  • dialkylammonium salts examples include di(1-propyl)ammoniumtetra(pentafluorophenyl)boron and dicyclohexylammoniumtetra(phenyl)boron.
  • ionic compounds are triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenylcyclopentadienyl complex, N,N-diethylaniliniumpentaphenylcyclopentadienyl complex and a boron compound represented by the formula (iv): wherein Et is an ethyl group, or the formula (v):
  • borane compounds examples include:
  • carborane compounds examples include:
  • the heteropoly compound comprises an atom of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
  • examples of such compounds include phosphovanadic acid, germanovanadic acid, arsenovanadic acid, phosphoniobic acid, germanoniobic acid, silicomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenomolybdic acid, stannomolybdic acid, phosphotungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotaungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdoniobic acid,
  • heteropoly compounds and isopoly compounds may be used singly or in combination of two or more kinds.
  • the ionizing ionic compounds (B-3) mentioned above may be used singly or in combination of two or more kinds.
  • the below-described carrier (C) can optionally be used by supporting at least one component selected from the above-mentioned reaction products (A1) to (A3) and transition metal compounds (A0) and (A4) to (A6) (referred to as “Component A” hereinafter) and/or at least one compound selected from the organometallic compound (B-1), the organoaluminum oxy-compound (B-2) and the ionizing ionic compound (B-3) (referred to as "Compound B” hereinafter).
  • the carrier (C) optionally used in the invention is an inorganic or organic compound in the form of granular or particulate solid.
  • the inorganic compounds porous oxides, inorganic chlorides, clay, clay minerals or ion-exchange layered compounds are preferable.
  • porous oxides examples include SiO 2 , Al 2 O 3 , MgO, ZrO, TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2 , and complex compounds or mixtures containing these oxides, such as natural or synthetic zeolite, SiO 2 -MgO, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 and SiO 2 -TiO 2 -MgO. Of these, preferable are compounds containing SiO 2 and/or Al 2 O 3 as the main component.
  • the inorganic oxides may contain small amounts of carbonate, sulfate, nitrate and oxide components, such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg(NO 3 ) 2 , Al(NO 3 ) 3 , Na 2 O, K 2 O and Li 2 O.
  • carbonate, sulfate, nitrate and oxide components such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , KNO 3 , Mg(NO 3 ) 2 , Al(NO 3 ) 3 , Na 2 O, K 2 O and Li 2 O.
  • the carrier preferably used in the invention has a particle diameter of 10 to 300 ⁇ m, preferably 20 to 200 ⁇ m, a specific surface area of 50 to 1,000 m 2 /g, preferably 100 to 700 m 2 /g, and a pore volume of 0.3 to 3.0 cm 3 /g. If necessary, the carrier may be calcined at 100 to 1,000 °C, preferably 150 to 700 °C, prior to use.
  • Examples of the inorganic chlorides employable in the invention include MgCl 2 , MgBr 2 , MnCl 2 and MnBr 2 .
  • the inorganic chloride may be used as it is, or may be used after pulverized by, for example, a ball mill or an oscillating mill.
  • the inorganic chloride may also be used as fine particles of a obtained by dissolving the inorganic chloride in a solvent such as alcohol and then precipitating using a precipitant.
  • the clay employable as a carrier in the invention is generally composed mainly of clay minerals.
  • the ion-exchange layered-compounds employable as a carrier in the invention is compounds having a crystal structure wherein planes formed by ionic bonding or the like are laminated in parallel to one another with a weak bond strength, and the ions contained therein are exchangeable. Most of clay minerals are ion-exchange layered compounds.
  • the clay, the clay minerals and the ion-exchange layered compounds employable in the invention are not limited to natural ones but include synthetic ones.
  • clay, clay minerals and ion-exchange layered compounds examples include clay, clay minerals and ion crystalline compounds having layered crystal structures such as hexagonal closest packing type, antimony type, CdCl 2 type and CdI 2 type.
  • the clay and the clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, mica, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, nacrite, dickite and halloysite.
  • ion-exchange layered compounds include crystalline acid salts of polyvalent metals, such as ⁇ -Zr (HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Zr(KPO 4 ) 2 ⁇ 3H 2 O, ⁇ -Ti(HPO 4 ) 2 , ⁇ -Ti(HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Sn(HPO 4 ) 2 ⁇ H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Ti(HPO 4 ) 2 and ⁇ -Ti (NH 4 PO 4 ) 2 ⁇ H 2 O,
  • polyvalent metals such as ⁇ -Zr (HAsO 4 ) 2 ⁇ H 2 O, ⁇ -Zr(HPO 4 ) 2 , ⁇ -Zr(KPO 4 ) 2 ⁇ 3H 2 O, ⁇ -Ti(HPO 4 ) 2 , ⁇ -Ti(HAs
  • the clay, the clay minerals, and the ion-exchange layered compounds are preferably those having a pore volume, as measured on pores having a radius of not less than 20 ⁇ by a mercury penetration method, of not less than 0.1 cc/g, and are particularly preferably those having a pore volume of 0.3 to 5 cc/g.
  • the pore volume is measured on the pores having a radius of 20 to 3 ⁇ 10 4 ⁇ by a mercury penetration method using a mercury porosimeter.
  • the clay and the clay minerals to be used in the invention are subjected to chemical treatments. Any of surface treatments, for example, to remove impurities attached to the surface and to influence on the crystal structure of the clay, are employable. Examples of such chemical treatments include acid treatment, alkali treatment, salt treatment and organic substance treatment.
  • the acid treatment can contribute to not only removing impurities from the surface but also eluting cations such as Al, Fe and Mg present in the crystal structure to increase the surface area.
  • the alkali treatment can destroy crystal structure of clay to bring about change in the structure of the clay.
  • the salt treatment and the organic substance treatment can produce, for example, ionic composites, molecular composites, or organic derivative to change the surface area or the distance between layers.
  • the ion-exchange layered compound for use in the invention may be a layered compound in which the exchangeable ions between layers have been exchanged with other large and bulky ions utilizing ion exchange properties to enlarge the distance between the layers.
  • the bulky ion plays a pillar-like roll to support the layer structure and is generally called a "pillar".
  • Introduction of other substances between layers of a layered compound is called "intercalation”.
  • guest compounds to be intercalated include cationic inorganic compounds, such as TiCl 4 and ZrCl 4 ; metallic alkoxides, such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 and B(OR) 3 (R is a hydrocarbon group or the like); and metallic hydroxide ions, such as [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ]2+ and [Fe 3 O(OCOCH 3 ) 6 ] + .
  • cationic inorganic compounds such as TiCl 4 and ZrCl 4
  • metallic alkoxides such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 and B(OR) 3 (R is a hydrocarbon group or the like
  • metallic hydroxide ions such as [Al 13 O 4 (OH) 24 ] 7+ , [Zr 4 (OH) 14 ]2+ and [Fe 3 O(OCOCH 3 ) 6
  • the compounds mentioned above may be used singly or in combination of two or more kinds.
  • the intercalation of the compounds may be carried out in the presence of polymers obtained by hydrolysis of metallic alkoxides such as Si(OR) 4 , Al(OR) 3 and Ge(OR) 4 (R is a hydrocarbon group or the like) or in the presence of colloidal inorganic compounds such as SiO 2 .
  • the pillars include oxides produced by intercalation of the above-mentioned metallic hydroxide ions between layers, followed by dehydration under heating.
  • the clay, clay minerals and ion-exchange layered compounds mentioned above may be used as they are, or may be used after they are subjected to a treatment of ball milling, sieving or the like. Moreover, they may be used after they are subjected to water adsorption or dehydration under heating.
  • the clay, clay minerals and ion-exchange layered compounds may be used singly or in combination of two or more kinds.
  • clay and clay minerals are preferable, and particularly preferable are montmorillonite, vermiculite, hectorite, tenorite and synthetic mica.
  • the organic compound is, for example, a granular or particulate solid compound having a particle diameter of 10 to 300 ⁇ m.
  • examples of such compounds include (co)polymers produced using an ⁇ -olefin of 2 to 14 carbon atoms such as ethylene, propylene, 1-butene or 4-methyl-1-pentene as a main ingredient, (co)polymers produced using vinylcyclohexane or styrene as a main ingredient, and modified products thereof.
  • the below-described specific organic compound component (D) may be optionally used.
  • the organic compound component (D) is optionally used to improve polymerizability and properties of the resulting polymer.
  • the organic compounds include alcohols, phenolic compounds, carboxylic acids, carboxylic acid esters, phosphorus compounds, sulfonates and halogenated hydrocarbons.
  • R 31 -OH As the alcohols and the phenolic compounds, those represented by R 31 -OH (R 31 is a hydrocarbon group of 1 to 50 carbon atoms or a halogenated hydrocarbon group of 1 to 50 carbon atoms) are generally employed.
  • Preferable alcohols are those wherein R 31 is a halogenated hydrocarbon group.
  • Preferable phenolic compounds are preferably those wherein the ⁇ , ⁇ '-positions to the hydroxyl group are substituted with hydrocarbon groups of 1 to 20 carbon atoms.
  • R 32 -COOH As the carboxylic acids, those represented by R 32 -COOH (R 32 is a hydrocarbon group of 1 to 50 carbon atoms or a halogenated hydrocarbon group of 1 to 50 carbon atoms, preferably a halogenated hydrocarbon group of 1 to 50 carbon atoms) are generally employed.
  • carboxylic acid esters alkyl or aryl esters of the carboxylic acids represented by R 32 -COOH are generally employed. Of these, desirable are carboxylic acid esters having halogenated hydrocarbon groups such as n-butyl perchlorocrotonate and ethyl trichloroacetate for the purpose to improve polymerizability.
  • the sulfonates used in the invention are those represented by the following formula:
  • M is an element of Group 1 to Group 14 of the periodic table.
  • R 33 is hydrogen, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms.
  • X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms.
  • n 1 to 7
  • chloroform and carbon tetrachloride are exemplified.
  • transition metal compounds other than the above mentioned transition metal compound (A0) and (A4) to (A6) can be used in combination.
  • Examples of the other transition metal compounds include the following compounds.
  • a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising the aforesaid components (A) and (B).
  • Fig. 1 shows an example of the preparation process of the olefin polymerization catalyst used in the present invention.
  • Non-polar olefin means the unsaturated hydrocarbon consisting of carbon atoms and hydrogen atoms only.
  • the non polar olefins include ⁇ -olefins of 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene; cycloolefins of 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene and tetracyclododecene; dienes or polyenes which are cyclic or chain compounds having two or more double bonds, and having 4 to 30 carbon atoms,
  • the polar olefins of the present invention are unsaturated hydrocarbons having polar groups. Examples thereof include:
  • unsaturated hydrocarbons having two or more of the above mentioned polar groups are employable.
  • examples thereof include vinylbenzoic acid, methylvinylbenzoate, vinylbenzylacetate, hydroxystyrene, 4-(3-butenyloxy)methyl benzoate, allyltrifluoroacetate, o-chlorostyrene, p-chlorostyrene, divinylbenzene, glycidylacrylate, allylglycidylether, (2H-perfluoropropyl)-2-propenylether, linalooloxide, 3-allyloxy-1,2-propanediol, 2-(allyloxy)ethanol, N-allylmorpholine, allylglycine, N-vinyl pyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl(diisopropylamino)silane, 7-ctenyltrimethoxys
  • the way of charging the component (A) into a polymerization reactor usage of each component, the feeding process and the order of feeding can be chosen as desired, but for reference, some examples are given below.
  • An olefin may be prepolymerized onto a solid catalyst component wherein the component (A) and, if necessary, the component (B) are supported on the carrier (C).
  • the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization or suspension polymerization, and gas phase polymerization.
  • a non-polar olefin or a polar olefin itself can be used as the solvent.
  • the component (A) may be used in an amount of usually 10 -12 to 10 -2 mol, preferably 10 -10 to 10 -3 mol, based on 1 liter of the reaction volume. In the present invention, even if the component (A) is used in a relatively low concentration, an olefin can be polymerized with a high polymerization activity.
  • the component (B-1) may be used in such an amount that the molar ratio of the component (B-1) to the transition metal atom (M or M') in the component (A) ((B-1)/ (M or M')) becomes usually 0.01 to 100,000, preferably 0.05 to 50,000.
  • the component (B-2) may be used in such an amount that the molar ratio of the aluminum atom in the component (B-2) to the transition metal atom (M or M') in the component (A) ((B-2)/(M or M')) becomes usually 10 to 500,000, preferably 20 to 100,000.
  • the component (B-3) may be used in such an amount that the molar ratio of the component (B-3) to the transition metal atom (M or M') in the component (A) ((B-3)/(M or M')) becomes usually 1 to 10, preferably 1 to 5.
  • the component (D) may be used, when the component (B) is the component (B-1), in such an amount that the molar ratio of (D)/(B-1) becomes usually 0.01 to 10, preferably 0.1 to 5; when the component (B) is the component (B-2), in such an amount that the molar ratio of (D)/(B-2) becomes usually 0.001 to 2, preferably 0.005 to 1; and when the component (B) is the component (B-3), in such an amount that the molar ratio of (D)/(B-3) becomes usually 0.01 to 10, preferably 0.1 to 5.
  • each amount of the non-polar olefin and the polar olefin used in the polymerization there is no specific restriction on each amount of the non-polar olefin and the polar olefin used in the polymerization, and each proper amount is determined according to the kind of olefin to be used and copolymerization ratio of the copolymer to be obtained.
  • the polymerization temperature may be in the range of usually -50 to 200 °C, preferably 0 to 170 °C.
  • the polymerization pressure may be in the range of usually atmospheric pressure to 100 kg/cm 2 , preferably atmospheric pressure to 50 kg/cm 2 .
  • the polymerization reaction can also be carried out by any of batchwise, semi-continuous and continuous processes. Further the polymerization can be conducted in two or more stages under different reaction-conditions.
  • the molecular weight of the resulting polar olefin copolymer can be regulated by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.
  • the molecular weight can also be regulated by changing the type of the component (B).
  • the polar olefin copolymer of the present invention as compared with conventional olefin polymers, has excellent adhesion properties, coating properties, compatibility, hydrophilic properties, oil resistance and the like, so that it can be used in such application fields that those characteristics are used effectively.
  • polar olefin copolymer of the present invention can also be used as modifiers by mixing with other polymers such as polyethylene, polypropylene and the like.
  • a polar olefin copolymer can be produced by copolymerizing a non-polar olefin and a polar olefin with a high polymerization activity.
  • the structures of the compounds obtained in the synthesis examples were determined by 270 MHz 1 H-NMR (Japan Electron Optics Laboratory GSH-270 Model), FT-IR (SHIMADZU FTIR-8200D Model), FD-mass spectrometry (Japan Electron Optics Laboratory SX-102A Model), metal content analysis (analysis by ICP method after dry ashing and dissolution in dilute nitric acid, device: SHIMADZU ICPS-8000 Model), and elemental analysis for carbon, hydrogen and nitrogen (Helaus CHNO Model).
  • the intrinsic viscosity ( ⁇ ) was measured in decalin at 135 °C.
  • the solution was dropwise added slowly to a mixture solution of 7.05 ml (0.5 mmol/ml-heptane solution, 3.53mmol) of a titanium tetrachloride solution and 40 ml of diethyl ether, said mixture having been cooled to -78 °C.
  • the reaction solution was slowly heated to room temperature with stirring.
  • the reaction solution was further stirred for another 8 hours at room temperature, and the solution was filtered through a glass filter to obtain a solid.
  • the solid was dissolved in and washed with 50 ml of methylene chloride, and the insolubles were removed.
  • the filtrate was concentrated under reduced pressure to precipitate a solid.
  • the resultant solution was dropwise added slowly to a mixture solution of 6.08 ml of a titanium tetrachloride solution (0.5 mmol/ml-heptane solution, 3.04 mmol) and 16 ml of diethyl ether, said mixture having been cooled to -78 °C.
  • the reaction solution was slowly heated to room temperature with stirring.
  • the reaction solution was further stirred for another 8 hours at room temperature, and the reaction solution was filtered through a glass filter.
  • the filtrate was concentrated under reduced pressure to precipitate a solid.
  • the solid was dissolved in 5 ml of methylene chloride, and 10 ml of hexane was slowly added to the solution with stirring.
  • the solution was dropwise added slowly to a mixture solution of 0.558 g (3.53 mmol) of chromium trichloride and 40 ml of THF, said mixture having been cooled to - 78°C. After the dropwise addition was completed, the reaction solution was slowly heated to room temperature with stirring. The reaction solution was further stirred for another 5 hours at room temperature, and the reaction solution was filtered through a glass filter to obtain a solid. The solid was dissolved in and washed with 50 ml of methylene chloride to remove insolubles. The filtrate was vacuum dried, and reprecipitated with ether/hexane to obtain a green powder. The powder was separated by filtration through a glass filter and washed with hexane.
  • the solution was dropwise added slowly to a solution 0.59 g (1.57 mmol) of VCl 3 (thf) 3 in 15 ml of diethylether, having been cooled to -0 °C. After the dropwise addition was completed, the reaction solution was slowly heated to room temperature with stirring. The reaction solution was further stirred for another 3 hours at room temperature. After the stirring, the solvent was distilled off under reduced pressure. Then the remained yellowish brown solid was extracted with 30 ml of methylene chloride. The extract was filtered through a glass filter to concentrate to about 10 ml, and then 15 ml of hexane was added thereto.
  • This compound was dissolved in 50 ml of THF at room temperature, and the resulting solution was dropwise added to 125 ml (2.86 mmol) of a vanadium trichloride THF solution (0.023 M) having been cooled to -78°C, with stirring. After the dropwise addition was completed, the reaction solution was heated to room temperature and stirred for 12 hours. Then, the solvent was removed under vacuum, and 50 ml of toluene was added at room temperature to prepare a solution. The solution was filtered through a glass filter to remove an inorganic salt contained in the solution. Then, the solution was concentrated to about 10 ml. To the solution, 80 ml of n-hexane was added, and they were stirred for one hour.
  • the reaction product was introduced into a large amount of methanol to precipitate a total amount of a polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was sufficiently washed with methanol, and then further vacuum dried at 80 °C for 10 hours to obtain 1.15 g of a polymer.
  • the polymer proved to be an ethylene/NDCA copolymer containing 0.02 mol% of NDCA.
  • the coordination energy difference ⁇ E was calculated under the conditions that in the chemical formulas (2) and (3) described above, the ligand L was a ligand of the complex (1), the number a of the ligands was 2, and the central metal M was Ti (IV). As a result, the coordination energy difference ⁇ E was 20.3 kJ/mol.
  • the polymer proved to be an ethylene/maleic anhydride copolymer containing 0.01 mol% of maleic anhydride.
  • the coordination energy difference ⁇ E was calculated under the conditions that in the chemical formulas (2) and (3) described above, the ligand L was a ligand of the complex (2), the number a of the ligands was 2, and the central metal M was Ti (IV). As a result, the coordination energy difference ⁇ E was 43.6 kJ/mol.
  • the reaction product was introduced into a large amount of methanol to precipitate a total amount of a polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was sufficiently washed with methanol, and then further vacuum dried at 80 °C for 10 hours to obtain 0.13 g of a polymer.
  • the polymer proved to be an ethylene/NDCA copolymer containing 0.02 mol% of NDCA.
  • the coordination energy difference ⁇ E was calculated under the conditions that in the chemical formulas (2) and (3) described above, the ligand L was a ligand of the complex (3), the number a of the ligands was 2, and the central metal M was Ti (IV). As a result, the coordination energy difference ⁇ E was 24.2 kJ/mol.
  • the reaction product was introduced into a large amount of methanol to precipitate a total amount of a polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was sufficiently washed with methanol, and then vacuum dried at 80 °C for 10 hours to obtain 0.38 g of a polymer.
  • the polymer proved to be an ethylene/NDCA copolymer containing 0.03 mol% of NDCA.
  • the coordination energy difference ⁇ E was calculated under the conditions that in the chemical formulas (2) and (3) described in claim 1, the ligand L was a ligand of the complex (4), the number a of the ligands was 2, and the central metal M was V (III). As a result, the coordination energy difference ⁇ E was -26.9 kJ/mol.
  • the polymer proved to be an ethylene/NDCA copolymer containing 0.02 mol% of NDCA.
  • the coordination energy difference ⁇ E was calculated under the conditions that in the chemical formulas (2) and (3) described in claim 1, the ligand L was a ligand of the complex (5), the number a of the ligands was 2, and the central metal M was V (IV). As a result, the coordination energy difference ⁇ E was 9.1 kJ/mol.
  • the polymer proved to be an ethylene/NDCA copolymer containing 0.02 mol% of NDCA.
  • the polymer proved to be an ethylene/maleic anhydride copolymer containing 0.02 mol% of maleic anhydride.
  • Example 2 Polymerization and after-treatments were carried out in the same manner as in Example 1, except that the complex (14) obtained in Synthesis Example 26 was used in place of the complex (1), the amount of NDCA was changed to 2.0 mmol, and the polymerization time was changed to 60 minutes. As a result, 0.03 g of a polymer was obtained. Then, measurements of IR and 13 C-NMR of the polymer obtained were carried out. As a result, the polymer proved to be an ethylene/NDCA copolymer containing NDCA in an amount of 0.02 mol based on 100 mol of the ethylene unit.
  • the coordination energy difference ⁇ E was calculated under the conditions that in the chemical formulas (2) and (3) described in claim 1, the ligand L was a cyclopentadienyl group, the number a of the ligands was 2, and the central metal M was Ti (IV). As a result, the coordination energy difference ⁇ E was 93.1 kJ/mol.
  • the reaction product was introduced into a large amount of methanol acidified with hydrochloric acid, to precipitate the whole polymer, followed by filtration through a glass filter.
  • the polymer was sufficiently washed with methanol and then vacuum dried at 80°C for 10 hours.
  • the yield of the polymer, ( ⁇ ) and a polar olefin content determined by 13 C-NMR are set forth in Table 1.
  • a polar olefin was contained, and the polymers obtained were ethylene/polar olefin copolymers.
  • Example10 Example11 Example12 Example13 Example14 Example15 Example16 Example17 polymerization conditions polar olefin type methyl acrylate 4-ethyl pentenoate norbomene carboxylate undecenol amount (mmol) 6 6 6 6 6 6 40 40 catalyst type complex(5) complex(5) complex(15) complex(5) complex(15) amount (mmol) 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.025 0.025 co-catalyst type DCL DCL DCL DOL DEAC DEAC DEAC DEAC amount (mmol) 8 8 8 8 8 50 50 etylene flow rate (L/hr) 100 100 100 100 100 100 100 100 100 100 100 2 2 polymerization time (min) 5 30 30 30 5 5 60 90 polymerization results polymer yield (g) 1.47 0.31 0.35 0.38 2.74 3.14 3.76 3.76 [ ⁇ ] (dl/g) 7.42 1.09 1.15 1.18 5.30 5.12 1.02 1.50 polar olefin content (mol%) 0.03 0.03
  • Example 10 The yield of the polymer, ( ⁇ ) and a methyl acrylate content determined by 13 C-NMR are set forth in Table 2, in which the results of Example 10 are also set forth. In all polymers obtained, methyl acrylate was contained, and the polymers obtained were ethylene/methyl acrylate copolymers. Table 2 Example 10 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 catalyst Complex (5) Complex (8) Complex (9) Complex (10) Complex(13) Complex(11) Complex (12) polymer yield(g) 1.47 0.07 2.15 0.5 1.48 1.77 0.89 [ ⁇ ] (dl/g) 7.42 7.56 7.38 7.58 8.24 7.15 7.26 methyl acrylate content (mol%) 0.03 0.05 0.02 0.08 0.02 0.07 0.05
  • the yield of the polymer, ( ⁇ ), and a propylene content and a methyl acrylate content determined by 13 C-NMR are set forth in Table 3.
  • methyl acrylate was contained, and the polymers obtained were ethylene/propylene/methyl acrylate copolymers.
  • the monomer-monomer sequence distribution of the copolymer obtained in Example 26 was measured by 13 C-NMR, and as a result, the copolymer had an ethylene-ethylene sequence proportion of 65.4 mol%, an ethylene-propylene sequence proportion of 32.0 mol%, an ethylene-methyl acrylate sequence proportion of 0.2 mol%, a propylene-propylene sequence proportion of 1.6 mol%, a propylene-methyl acrylate sequence proportion of 0.7 mol% and a methyl acrylate-methyl acrylate sequence proportion of 0.1 mol%.
  • Example 26 Polymerization and after-treatments were carried out in the same manner as in Example 26, except that 4 mmol of ethyl trichloroacetate was added after the addition of ethylaluminum dichloride. As a result, 2.76 g of a polymer was obtained. Then, measurement of 13 C-NMR of the polymer obtained was carried out, and as a result, the polymer proved to be an ethylene/propylene/methyl acrylate copolymer containing 1.6 mol% of methyl acrylate. The propylene content was 11.6 mol%, and ( ⁇ ) was 1.75 dl/g.
  • Example 26 Polymerization and after-treatments were carried out in the same manner as in Example 26, except that a mixed gas obtained by further adding 20 1/hr of hydrogen to the ethylene/propylene mixed gas was used. As a result, 2.37 g of a polymer was obtained. Then, measurement of 13 C-NMR of the polymer obtained was carried out, and as a result, the polymer proved to be an ethylene/propylene/methyl acrylate copolymer containing 0.6 mol% of methyl acrylate. The propylene content was 19.4 mol%, and ( ⁇ ) was 2.31 dl/g.
  • a sheet (thickness: 100 ⁇ m) of the copolymer obtained in Example 30 was prepared, and the sheet was cut into a strip.
  • the strip was interposed between aluminum foils (thickness: 50 ⁇ m) having the same width as that of the strip, and they were heat-sealed at 200°C for 5 seconds by a heat sealer. From the sealed portion, a strip having a width of 15 mm was cut out, and the peel strength was measured under the conditions of a peel angle of 180° and a peel rate of 200 m/min. As a result, the peel strength was 0.90 kg/15 min.
  • the peel strength of an ethylene/propylene copolymer (propylene content: 18.4 mol%, ( ⁇ ): 2.29 dl/g) containing no methyl acrylate was measured in the same manner as described above. As a result, the peel strength was 0.08 kg/15 min.
  • Example 30 It was proved that the ethylene/propylene/methyl acrylate copolymer obtained in Example 30 had a higher peel strength and higher adhesion properties to aluminum.
  • a film of the copolymer obtained in Example 30 was prepared using a hot toluene solution of the copolymer.
  • the film was subjected to a droplet method to measure a forward contact angle and a backward contact angle of the copolymer against water. As a result, the forward contact angle was 60°, and the backward contact angle was 93°.
  • the forward contact angle and the backward contact angle of an ethylene/propylene copolymer (propylene content: 18.4 mol%, ( ⁇ ): 2.29 dl/g) containing no methyl acrylate was measured in the same manner as described above. As a result, the forward contact angle was 88°, and the backward contact angle was 105°.
  • Example 30 It was proved that the ethylene/propylene/methyl acrylate copolymer obtained in Example 30 had smaller contact angles and higher wetting properties to water.
EP06021629A 2000-07-04 2001-07-04 Procédé de préparation d'un copolymère à base d'une oléfine non-polaire et d'une oléfine polaire, et le copolymère ainsi obtenu Withdrawn EP1832609A3 (fr)

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